Intermolecular configurations dominated by quadrupole-quadrupole electrostatic interactions: explicit correlation treatment of the five-dimensional potential energy surface and infrared spectra for the CO-N 2 complex.

A thorough understanding of the intermolecular configurations of van der Waals complexes is a great challenge due to their weak interactions, floppiness and anharmonic nature. Although high-resolution microwave or infrared spectroscopy provides one of the most direct and precise pieces of experimental evidence, the origin and key role in determining such intermolecular configurations of a van der Waals system strongly depend on its highly accurate potential energy surface (PES) and a detailed analysis of its ro-vibrational wavefunctions. Here, a new five-dimensional potential energy surface for the van der Waals complex of CO-N2 which explicitly incorporates the dependence on the stretch coordinate of the CO monomer is generated using the explicitly correlated couple cluster (CCSD(T)-F12) method in conjunction with a large basis set. Analytic four-dimensional PESs are obtained by the least-squares fitting of vibrationally averaged interaction energies for v = 0 and v = 1 to the Morse/Long-Range potential mode (VMLR ). These fits to 7966 points have root-mean-square deviations (RMSD) of 0.131 cm-1 and 0.129 cm-1 for v = 0 and v = 1, respectively, with only 315 parameters. Energy decomposition analysis is carried out, and it reveals that the dominant factor in controlling intermolecular configurations is quadrupole-quadrupole electrostatic interactions. Moreover, the rovibrational levels and wave functions are obtained for the first time. The predicted infrared transitions and intensities for the ortho-N2 -CO complex as well as the calculated energy levels for para-N2 -CO are in good agreement with the available experimental data with RMSD discrepancies smaller than 0.068 cm-1 . The calculated infrared band origin shift associated with the fundamental band frequency of CO is -0.721 cm-1 for ortho-N2 -CO which is in excellent agreement with the experimental value of -0.739 cm-1 . The agreement with experimental values validates the high quality of the PESs and enhances our confidence to explain the observed mystery lines around 2163 cm-1 .